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  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/70—Iron group metals, platinum group metals or compounds thereof
  • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
  • C08F4/7039—Tridentate ligand
  • C08F4/704—Neutral ligand
  • C08F4/7042—NNN
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
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  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
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  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
  • C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
  • C07C2531/30—Halides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present disclosure relates to a field of olefin polymerization, in particular to a catalyst composition used in a process of ethylene oligomerization.
• the present disclosure further relates to use of the catalyst composition.
• Linear alpha olefins are widely used in a wide range of applications, such as ethylene comonomers, intermediates in production of surfactants, plasticizer alcohols, synthetic lubricants and oil additives, etc.
• LAOS Linear alpha olefins
• iron (II) and cobalt (II) based catalysts bearing imino-pyridyl tridentate ligands for catalyzing ethylene oligomerization have been reported respectively by Brookhart's group (see Brookhart M. et al, J. Am. Chem. Soc., 1998, 120, 7143-7144, and WO99/02472) and Gibson's group (see Gibson V. C. et al, Chem. Commun., 1998, 849-850, and Chem. Eur. J., 2000, 2221-2231), in which both the catalytic activity and selectivity of alpha olefins are high.
• the present disclosure expects to provide a technical solution that can overcome prejudices against water in the prior art relating to the oligomerization process.
• a catalyst composition containing water is provided for ethylene oligomerization, a high oligomerization activity can actually be obtained even at a rather low ratio of aluminum to iron and/or a low temperature.
• the inventor of the present disclosure has conducted extensive and in-depth researches, and surprisingly found that a high oligomerization activity can be obtained using a catalyst composition containing an imino ferrous complex shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• the catalyst composition can even enable a high oligomerization activity at a rather low ratio of Al/Fe.
• the oligomerization reaction is of rapid initiation, stable operation, and good repeatability.
• a catalyst composition for ethylene oligomerization comprising an imino ferrous complex as shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent:
• R is selected from hydrogen, oxygen, and (C 1 -C 10 ) linear alkyl, (C 3 -C 10 ) branched alkyl, (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups.
• R′ is selected from substituted or unsubstituted (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, (C 7 -C 20 ) alkaryl groups.
• R and R′ is optionally bonded to or not to form a ring.
• R is selected from hydrogen, oxygen, and (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups; and R′ is selected from substituted or unsubstituted phenyl, naphthyl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups.
• R 6 is selected from hydrogen, and saturated or unsaturated (C 1 -C 3 ) hydrocarbyl groups.
• R 7 is selected from saturated or unsaturated (C 1 -C 3 ) hydrocarbyl groups, R 6 and R 7 optionally being bonded to or not to form a ring.
• R 8 is selected from saturated or unsaturated (C 1 -C 3 ) hydrocarbyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups.
• R 7 and R 8 are optionally bonded to or not to form a ring.
• the catalyst composition based on weight of the organic solvent, has a content of water in the range from 5 to 450 ppm, preferably from 5 to 350 ppm, more preferably 20 to 260 ppm, and further preferably from 50 to 200 ppm.
• the main catalyst imino ferrous complex has a general formula as shown in Formula (II):
• R is selected from hydrogen, oxygen, and (C 1 -C 10 ) linear alkyl, (C 3 -C 10 ) branched alkyl, (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups, preferably from hydrogen, and (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups; and R′ is selected from substituted or unsubstituted (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, (C 7 -C 20 ) alkaryl groups, preferably from substituted or unsubstituted phenyl, naphthyl, (C 7 -C 20 )
• the main catalyst imino ferrous complex has a general formula as shown in Formula (III):
• R 1 to R 5 each are independently selected from hydrogen, (C 1 -C 6 ) alkyl groups, halogens, (C 1 -C 6 ) alkoxy or nitro groups; and R is selected from hydrogen, (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups.
• R is selected from hydrogen, and methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, phenyl, benzyl, tolyl, and phenethyl groups.
• R 1 to R 5 each are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl groups, fluorine, chlorine, bromine, and methoxyl, ethoxyl and nitro groups.
• R 1 and R 5 are both ethyl groups, and R 2 to R 4 all hydrogen.
• the main catalyst imino ferrous complex has a general formula as shown in Formula (IV):
• R 7 is selected from (C 1 -C 5 ) alkyl groups.
• R is selected from hydrogen, oxygen, and (C 1 -C 5 ) alkyl groups.
• R 1 to R 5 each are independently selected from hydrogen, (C 1 -C 6 ) alkyl groups, halogens, and (C 1 -C 6 ) alkoxy or nitro groups.
• R is optionally bounded to R 1 or to a carbon atom connected to R 1 to or not to form a ring.
• R 1 to R 5 each are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl groups, fluorine, chlorine, bromine, and methoxyl, ethoxyl and nitro groups.
• R 1 and R 5 are both selected from hydrogen, and methyl and ethyl groups, and R 2 to R 4 are each hydrogen.
• R 1 is hydrogen, R is bounded to a carbon atom connected to R 1 to or not to form a ring.
• the molar ratio of aluminum in the cocatalyst to iron in the main catalyst ranges from 30:1 to less than 900:1, preferably from 100:1 to 700:1, and more preferably from 148:1 to 196:1.
• the aluminum-containing cocatalyst is selected from aluminoxanes and alkylaluminum compounds, preferably from alkylaluminum compounds.
• the alkylaluminum compounds are preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, and ethyl aluminum dichloride, more preferably triethylaluminum.
• the aluminoxanes are (C 1 -C 4 ) alkylaluminoxanes with linear or branched (C 1 -C 4 ) alkyl groups, preferably selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutyl aluminoxane, and more preferably methylaluminoxane.
• the catalyst composition of the present disclosure based on volume of the organic solvent, the catalyst composition has a content of the main catalyst in the range from 2 to 500 ⁇ mol, preferably from 20 to 100 ⁇ mol/L.
• the organic solvent is selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and dichloromethane, preferably from toluene and xylene.
• the present disclosure provides a process for ethylene oligomerization, comprising performing the ethylene oligomerization in the presence of the catalyst composition according to the first aspect of the present disclosure, wherein the catalyst composition comprises an imino ferrous complex as shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• the catalyst composition comprises an imino ferrous complex as shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• the process is performed at a temperature in the range from ⁇ 20° C. to 150° C., preferably from 0° C. to 80° C., and more preferably from 5° C. to 35° C.
• the reaction can be performed at a temperature in the range from 5° C. to 50° C.
• the process comprises mixing the main catalyst and the cocatalyst under ethylene atmosphere.
• a higher oligomerization activity can be obtained with the catalyst composition according to the present disclosure which comprises the imino ferrous complex shown in Formula (I) as the main catalyst, the aluminum-containing cocatalyst, water, and the organic solvent, than with a catalyst composition system in the prior art which contains no water.
• the catalyst composition according to the present disclosure when used, a high selectivity of ⁇ -olefins is obtainable.
• the catalyst composition according to the present disclosure can enable rapid initiation, stable operation, and good repeatability of the oligomerization reaction. According to the present disclosure, a high oligomerization activity can be obtained even at a rather low ratio of Al/Fe, or at a low reaction temperature.
• the present disclosure overcomes technical prejudices held by persons skilled in the art and achieves unexpected technical effects.
• a catalyst composition for ethylene oligomerization comprising an imino ferrous complex shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• R is selected from hydrogen, oxygen, and (C 1 -C 10 ) linear alkyl, (C 3 -C 10 ) branched alkyl, (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups; and R′ is selected from substituted or unsubstituted (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, (C 7 -C 20 ) alkaryl groups, R and R′ optionally being bonded to or not to form a ring.
• R 6 is selected from hydrogen and saturated or unsaturated (C 1 -C 5 ) hydrocarbyl groups
• R 7 is selected from saturated or unsaturated (C 1 -C 5 ) hydrocarbyl groups, R 6 and R 7 optionally being bonded to or not to form a ring
• R 8 is selected from saturated or unsaturated (C 1 -C 5 ) hydrocarbyl, (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups, R 7 and R 8 optionally being bonded to or not to form a ring.
• R is selected from hydrogen, oxygen, and (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups; and R′ is selected from substituted or unsubstituted phenyl, naphthyl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups.
• R 6 is selected from hydrogen, and saturated or unsaturated (C 1 -C 3 ) hydrocarbyl groups
• R 7 is selected from saturated or unsaturated (C 1 -C 3 ) hydrocarbyl groups, R 6 and R 7 optionally being bonded to or not to form a ring
• R 8 is selected from saturated or unsaturated (C 1 -C 3 ) hydrocarbyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups, R 7 and R 8 optionally being bonded to or not to form a ring.
• the catalyst composition according to the present disclosure contains water, but, when used in an ethylene oligomerization process, can lead to a high reaction activity, and rapid initiation, stable operation, and good repeatability of the reaction, with a high selectivity of ⁇ -olefins.
• anhydrous environment is not only unnecessary, but a certain amount of water is actually required to be added into the organic solvent to accomplish corresponding reactions.
• the catalyst composition according to the present disclosure promotes a high ethylene oligomerization activity and high selectivity of ⁇ -olefins.
• saturated or unsaturated (C 1 -C 5 ) hydrocarbyl groups refers to saturated or unsaturated hydrocarbyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, vinyl, propyl, isopropyl, allyl, propenyl, butyl, isobutyl, tert-butyl, and butenyl groups, etc.
• the catalyst composition based on weight of the organic solvent, the catalyst composition has a content of water in the range from 5 to 450 ppm (i.e., based on 1 g of the organic solvent, 5 ⁇ 10 ⁇ 6 to 450 ⁇ 10 ⁇ 6 g of water is contained in the catalyst composition), preferably from 5 to 350 ppm, more preferably 20 to 260 ppm, and further preferably from 50 to 200 ppm.
• the catalyst composition having water within the above content ranges, promotes even higher activity of ethylene oligomerization.
• the amount of the main catalyst and that of the cocatalyst can be selected according to actual process conditions such as the production scale, equipment, etc.
• the catalyst composition based on volume of the organic solvent, the catalyst composition has a content of the main catalyst in the range from 2 ⁇ mol/L to 500 ⁇ mol/L (i.e., based on 1 L of the organic solvent, the catalyst composition contains 2 ⁇ 10 ⁇ 6 mol to 500 ⁇ 10 ⁇ 6 mol of the main catalyst), preferably from 20 ⁇ mol/L to 100 ⁇ mol/L.
• the main catalyst imino ferrous complex has a general formula as shown in Formula (II).
• R is selected from hydrogen, oxygen, and (C 1 -C 10 ) linear alkyl, (C 3 -C 10 ) branched alkyl, (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, and (C 7 -C 20 ) alkaryl groups, preferably from hydrogen, and (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups; and R′ is selected from substituted or unsubstituted (C 6 -C 20 ) aryl, (C 7 -C 20 ) aralkyl, (C 7 -C 20 ) alkaryl groups, preferably from substituted or unsubstituted phenyl, naphthyl, (C 7 -C 20 )
• Said (C 7 -C 20 ) aralkyl groups comprise diphenyl methyl group.
• the structure as shown in Formula (II) is formed when both R 6 and R 7 , and R 7 and R 8 in Formula (I) are bonded to form benzene rings.
• the main catalyst imino ferrous complex has a general formula as shown in Formula (III).
• R 1 to R 5 each are independently selected from hydrogen, (C 1 -C 6 ) alkyl groups, halogens, (C 1 -C 6 ) alkoxy or nitro groups; and R is selected from hydrogen, (C 1 -C 5 ) linear alkyl, (C 3 -C 6 ) branched alkyl, (C 6 -C 10 ) aryl, (C 7 -C 10 ) aralkyl, and (C 7 -C 10 ) alkaryl groups. That is, when R′ in Formula (II) is an alkyl phenyl group, the structure as shown in Formula (III) can be obtained.
• R in Formula (III), R can be selected from hydrogen, and methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, phenyl, benzyl, tolyl, and phenethyl groups; and R 1 to R 5 each are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl groups, fluorine, chlorine, bromine, and methoxyl, ethoxyl and nitro groups, preferably, R 1 and R 5 both being ethyl groups, and R 2 to R 4 all hydrogen.
• (C 1 -C 6 ) alkyl groups refers to saturated linear or branched alkyl groups with 1-6 carbon atoms.
• Said (C 1 -C 6 ) alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, n-hexyl, and sec-hexyl groups, preferably methyl, ethyl, n-propyl, and isopropyl groups.
• (C 1 -C 6 ) alkoxyl groups refers to the groups obtained from the bond of a (C 1 -C 6 ) alkyl group with an oxygen atom.
• Said (C 1 -C 6 ) alkoxyl groups include methoxyl, ethoxyl, n-propoxyl, isopropoxyl, n-butoxyl, isobutoxyl, sec-butoxyl, tert-butoxyl, n-pentoxyl, sec-pentoxyl, n-hexyloxyl, and sec-hexyloxyl groups, preferably methoxyl and ethoxyl groups.
• halogens includes F, Cl, Br, and I, preferably F, Cl, and Br.
• the main catalyst imino ferrous complex as shown in Formula (III) has one of the following structures.
• the main catalyst imino ferrous complex has a general formula as shown in Formula (IV).
• R 7 is selected from (C 1 -C 5 ) alkyl groups; R is selected from hydrogen, oxygen, and (C 1 -C 5 ) alkyl groups; and R 1 to R 5 each are independently selected from hydrogen, (C 1 -C 6 ) alkyl groups, halogens, and (C 1 -C 6 ) alkoxy or nitro groups, R being optionally bounded to R 1 or to a carbon atom connected to R 1 to or not to form a ring.
• R 8 and R′ in Formula (I) are alkyl phenyl groups, and R 6 in Formula (I) is hydrogen, the structure as shown in Formula (IV) can be obtained.
• R 1 to R 5 each are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl groups, fluorine, chlorine, bromine, and methoxyl, ethoxyl and nitro groups.
• R 1 and R 5 are both selected from hydrogen, and methyl and ethyl groups, and R 2 to R 4 are each hydrogen.
• R 1 is hydrogen, R is bounded to a carbon atom connected to R 1 to or not to form a ring.
• the main catalyst imino ferrous complex as shown in Formula (IV) has one of the following structures.
• the molar ratio of aluminum in the cocatalyst to iron in the main catalyst ranges from 30:1 to less than 900:1, preferably from 100:1 to 700:1, and more preferably from 148:1 to 196:1.
• the aluminum-containing cocatalyst is selected from aluminoxanes and alkylaluminum compounds, preferably from alkylaluminum compounds.
• the alkylaluminum compounds are preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, and ethyl aluminum dichloride, more preferably triethylaluminum.
• the aluminoxanes are (C 1 -C 4 ) alkylaluminoxanes with linear or branched (C 1 -C 4 ) alkyl groups, preferably selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutyl aluminoxane, and more preferably methylaluminoxane.
• the catalyst composition of the present disclosure based on volume of the organic solvent, the catalyst composition has a content of the main catalyst in the range from 2 ⁇ mol/L to 500 ⁇ mol/L, preferably from 20 ⁇ mol/L, to 100 ⁇ mol/L.
• the organic solvent is selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and dichloromethane, preferably from toluene and xylene.
• CN 102558243A for synthesis of the compounds as shown in Formula (II) or (III).
• CN 102558243A is incorporated into the present disclosure as a reference.
• the main catalyst 2-acetyl-1,10-phenanthroline aminal ferrous chloride complex as shown in Formula (ii) can be prepared by the process as disclosed in CN 102485733A with specific steps as follows.
• Step a synthesis of 2-acetyl-1,10-phenanthroline: 1,10-phenanthroline is reacted with Et 3 Al. The resultant thereof successively goes through a hydrolysis reaction and then an oxidation reaction with nitrobenzene to obtain a compound as shown in Formula (b).
• 1,10-phenanthroline is first reacted with Et 3 Al in the presence of an organic solvent, which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• an organic solvent which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• a 1,10-phenanthroline solution with a concentration of 10 g/L to 200 g/L is prepared with the above organic solvents.
• the reaction between 1,10-phenanthroline and Et 3 Al is commonly performed at a temperature in the range from ⁇ 60° C.
• anhydrous or hydrous 1,10-phenanthroline, preferably anhydrous 1,10-phenanthroline, and Et 3 Al per se are selected as the raw materials for the above reaction with a molar ratio of 1,10-phenanthroline to Et 3 Al in the range from 1:0.5 to 1:4.5, preferably 1:2.0 to 1:2.6.
• the reaction is carried out usually by adding, for example, dropwise adding Et 3 Al at a reaction temperature into the 1,10-phenanthroline solution.
• the resulting mixture is stirred for 18 h to 28 h at the reaction temperature, preferably 18 to 20 h. Afterwards, the reaction temperature is heated up to 20° C. to 40° C., before the resulting mixture is stirred again for 5 h to 10 h, preferably 10 h to facilitate more complete reaction.
• water preferably deionized water
• water preferably deionized water
• water, preferably deionized water can be added into the resulting mixture at ⁇ 30° C. for hydrolysis. There are bubbles during hydrolysis process, and the hydrolysis process is not to be stopped until no bubbles come out.
• the resulting mixture is heated again to 20° C. to 40° C. and stirred for 5 h to 10 h. Subsequently, the resultant is separated and an organic phase therein is taken out.
• an organic solvent is preferably used for extraction of the inorganic phase in the resultant, and then the obtained organic phase is combined with the organic phase obtained through separation, wherein useful organic solvents can be ethyl acetate, acetone, dichloromethane, or a mixture thereof, preferably dichloromethane.
• the solvent is removed from the organic phase or combined organic phase under reduced pressure prior to addition of nitrobenzene therein for reflux (for example at 210° C.) for 10 h to 48 h, preferably 15 h to 24 h. After that, the resultant is filtered, and the solvent is removed under reduced pressure.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio therebetween in the range from 1:1 to 1:5, preferably 1:2 is used as an eluent to perform silica column chromatography to obtain a solid product, i.e., the compound as shown in Formula (b).
• the molar ratio of 1,10-phenanthroline to nitrobenzene is in the range from 1:0.5 to 1:30, preferably from 1:15 to 1:20.
• Step b synthesis of 2-acetyl-1,10-phenanthroline aminal ligand: the compound as shown in Formula (b) is reacted with the compound as shown in Formula (c) in the presence of p-toluenesulfonic acid as the catalyst to obtain the compound as shown in Formula (d).
• the product ligand as shown in Formula (d) is prepared by reacting 2-acetyl-1,10-phenanthroline obtained in Step a with substituted anline as shown in Formula (c) in a container in the presence of an organic solvent containing no water or oxygen, wherein the molar ratio of 2-acetyl-1,10-phenanthroline to substituted anline as shown in Formula (c) is in the range from 1:1 to 1:5.
• Said organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• the reaction is carried out under reflux in the presence of p-toluenesulfonic acid (p-TsOH) as the catalyst at, for example 110° C., wherein the mass ratio of p-TsOH to the total amounts of the reactants (i.e., the compounds as shown in Formulae (b) and (c)) is in the range from 0.001:1 to 0.02:1; and the reaction time is in the range from 5 h to 10 h.
• the reaction is monitored by TLC.
• the solvent is removed under reduced pressure.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio therebetween in the range from 1:1 to 1:9, preferably 1:4 is used as an eluent to perform silica column chromatography to obtain the target product, i.e., the compound as shown in Formula (d).
• the target product is characterized by nuclear magnetism and mass spectrum.
• the substituted anline as shown in Formula (c) can be an anline substituted by 1 to 5, preferably 1 to 4, and more preferably 1 to 3 identical or different substituent groups selected from (C 1 -C 6 ) alkyl and (C 1 -C 6 ) alkoxy groups, halogens, and nitro groups, for example, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethyl aniline, 2,4,6-trimethyl aniline, 4-bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diethylaniline, 2,6-diisopropyl aniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro
• Step c synthesis of 2-acetyl-1,10-phenanthroline aminal ferrous chloride complex: the compound as shown in Formula (d) is reacted with ferrous chloride to obtain the compound as shown in Formula (ii).
• ferrous chloride is dissolved into an organic solvent containing no water or oxygen, so as to form a solution with a concentration of 0.001 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• hydrated ferrous chloride FeCl 2 .4H 2 O
• 2-acetyl-1,10-phenanthroline aminal ligand (d) is separately dissolved into an organic solvent containing no water or oxygen to form a solution with a concentration of 0.01 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• the above two solutions are combined (for example at room temperature) under protection of an inner gas such as nitrogen, and the resulting mixture is stirred for some time under protection of an inert gas such as nitrogen, for example, being stirred overnight at room temperature.
• the reaction is monitored by TLC.
• conventional treatment methods of suction filtration, washing, drying, etc. are adopted to treat the reaction product to obtain the compound ligand as shown in Formula (ii). Said washing can be performed using an organic solvent such as anhydrous diethyl ether.
• the ligand is characterized by elemental analysis and infrared spectroscopy.
• the molar ratio of 2-acetyl-1,10-phenanthroline aminal ligand (d) to ferrous chloride is in the range from 1:1 to 1.2:1, preferably from 1.05:1 to 1.1:1.
• the main catalyst as shown in Formula (iv) can be prepared by the process as disclosed in CN 102558242A. Therefore, 2-isobutyryl-1,10-phenanthroline aminal ferrous chloride complex can be prepared by specific steps as follows.
• Step a synthesis of 2-isobutyryl-1,10-phenanthroline: 1,10-phenanthroline is reacted with (i-C 4 H 9 ) 3 Al. The resultant thereof successively goes through a hydrolysis reaction and then an oxidation reaction with nitrobenzene to obtain a compound as shown in Formula (b′).
• 1,10-phenanthroline is first reacted with (i-C 4 H 9 ) 3 Al in the presence of an organic solvent, which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• an organic solvent which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• a 1,10-phenanthroline solution with a concentration of 10 g/L to 200 g/L is prepared with the above organic solvents.
• the reaction between 1,10-phenanthroline and (i-C 4 H 9 ) 3 Al is commonly performed at a temperature in the range from ⁇ 60° C. to ⁇ 80° C., preferably from ⁇ 60° C. to ⁇ 70° C., favorably under protection of an inert gas, which is preferably selected as argon or nitrogen.
• Anhydrous or hydrous 1,10-phenanthroline, preferably anhydrous 1,10-phenanthroline, and (i-C 4 H 9 ) 3 Al per se are selected as the raw materials for the above reaction with a molar ratio of 1,10-phenanthroline to (i-C 4 H 9 ) 3 Al in the range from 1:0.5 to 1:4.5, preferably 1:2.0 to 1:2.6.
• the reaction is carried out usually by adding, for example, dropwise adding (i-C 4 H 9 ) 3 Al at a reaction temperature into the 1,10-phenanthroline solution.
• the resulting mixture is stirred for 18 h to 28 h at the reaction temperature, preferably 18 to 20 h.
• the reaction temperature is heated up to 20° C. to 40° C., before the resulting mixture is stirred again for 5 h to 10 h, preferably 10 h to facilitate more complete reaction.
• water preferably deionized water
• hydrolysis is added for hydrolysis at a temperature in the range from ⁇ 60° C. to 0° C.
• water preferably deionized water
• water can be added into the resulting mixture at ⁇ 30° C. for hydrolysis. There are bubbles during hydrolysis process, and the hydrolysis process is not to be stopped until no bubbles come out.
• the resulting mixture is heated again to 20° C. to 40° C. and stirred for 5 h to 10 h. Subsequently, the resultant is separated and an organic phase therein is taken out.
• an organic solvent is preferably used for extraction of the inorganic phase in the resultant, and then the organic phase is combined with the organic phase obtained through separation, wherein useful organic solvents can be ethyl acetate, acetone, dichloromethane, or a mixture thereof, preferably dichloromethane.
• the solvent is removed from the organic phase or combined organic phase under reduced pressure prior to addition of nitrobenzene therein for reflux (for example at 210° C.) for 10 h to 48 h, preferably 15 h to 24 h. After that, the resultant is filtered, and the solvent is removed under reduced pressure.
• the molar ratio of 1,10-phenanthroline to nitrobenzene is in the range from 1:0.5 to 1:30, preferably from 1:15 to 1:20.
• Step b synthesis of 2-isobutyryl-1,10-phenanthroline aminal ligand: the compound as shown in Formula (b′) is reacted with the compound as shown in Formula (c) in the presence of p-toluenesulfonic acid as the catalyst to obtain the compound as shown in Formula (d′).
• the product ligand as shown in Formula (d′) is prepared by reacting 2-isobutyryl-1,10-phenanthroline obtained in Step a with substituted anline as shown in Formula (c) in a container in the presence of an organic solvent containing no water or oxygen, wherein the molar ratio of 2-isobutyryl-1,10-phenanthroline to substituted anline as shown in Formula (c) is in the range from 1:1 to 1:5.
• Said organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• the reaction is carried out under reflux in the presence of p-toluenesulfonic acid (p-TsOH) as the catalyst at, for example 110° C., wherein the mass ratio of p-TsOH to the total amount of the reactants (i.e., the compounds as shown in Formulae (b′) and (c)) is in the range from 0.001:1 to 0.02:1; and the reaction time is in the range from 5 h to 10 h.
• the reaction is monitored by TLC.
• the solvent is removed under reduced pressure.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio therebetween in the range from 1:1 to 1:9, preferably 1:4 is used as an eluent to perform silica column chromatography to obtain the target product, i.e., the compound as shown in Formula (d′).
• the target product is characterized by nuclear magnetism and mass spectrum.
• Step c synthesis of 2-isobutyryl-1,10-phenanthroline aminal ferrous chloride complex: the compound as shown in Formula (d′) is reacted with ferrous chloride to obtain the compound as shown in Formula (iv).
• ferrous chloride is dissolved into an organic solvent containing no water or oxygen, so as to form a solution with a concentration of 0.001 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• hydrated ferrous chloride FeCl 2 .4H 2 O
• ferrous chloride can also be used instead of ferrous chloride.
• 2-isobutyryl-1,10-phenanthroline aminal ligand (d′) is separately dissolved into an organic solvent containing no water or oxygen to form a solution with a concentration of 0.01 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• the above two solutions are combined (for example at room temperature) under protection of an inner gas such as nitrogen, and the resulting mixture is stirred for some time under protection of an inert gas such as nitrogen, for example, being stirred overnight at room temperature.
• the reaction is monitored by TLC.
• conventional treatment methods of suction filtration, washing, drying, etc. are adopted to treat the reaction product to obtain the compound ligand as shown in Formula (iv). Said washing can be performed using an organic solvent such as anhydrous diethyl ether.
• the ligand is characterized by elemental analysis and infrared spectroscopy.
• the molar ratio of 2-isobutyryl-1,10-phenanthroline aminal ligand (d′) to ferrous chloride is in the range from 1:1 to 1.2:1, preferably from 1.05:1 to 1.1:1.
• the main catalyst as shown in Formula (iii) can be prepared by the process as disclosed in CN 102558241A. Therefore, 2-n-propyl-acyl-1,10-phenanthroline aminal ferrous chloride complex can be prepared by the specific steps as follows.
• Step a synthesis of 2-n-propyl-acyl-1,10-phenanthroline: 1,10-phenanthroline is reacted with (n-C 3 H 7 ) 3 Al. The resultant thereof successively goes through a hydrolysis reaction and then oxidation reaction with nitrobenzene to obtain a compound as shown in Formula (b′′).
• 1,10-phenanthroline is first reacted with (n-C 3 H 7 ) 3 Al in the presence of an organic solvent, which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• an organic solvent which can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• a 1,10-phenanthroline solution with a concentration of 10 g/L to 200 g/L is prepared with the above organic solvents.
• the reaction between 1,10-phenanthroline and (n-C 3 H 7 ) 3 Al is commonly performed at a temperature in the range from ⁇ 60° C. to ⁇ 80° C., preferably from ⁇ 60° C. to ⁇ 70° C., favorably under protection of an inert gas, which is preferably selected as argon or nitrogen.
• Anhydrous or hydrous 1,10-phenanthroline, preferably anhydrous 1,10-phenanthroline, and (n-C 3 H 7 ) 3 Al per se are selected as the raw materials for the above reaction with a molar ratio of 1,10-phenanthroline to (n-C 3 H 7 ) 3 Al in the range from 1:0.5 to 1:4.5, preferably 1:2.0 to 1:2.6.
• the reaction is carried out usually by adding, for example, dropwise adding (n-C 3 H 7 ) 3 Al at a reaction temperature into the 1,10-phenanthroline solution.
• the resulting mixture is stirred for 18 h to 28 h at the reaction temperature, preferably 18 to 20 h.
• the reaction temperature is heated up to 20° C. to 40° C., before the resulting mixture is stirred again for 5 h to 10 h, preferably 10 h to facilitate more complete reaction.
• water preferably deionized water
• hydrolysis is added for hydrolysis at a temperature in the range from ⁇ 60° C. to 0° C.
• water preferably deionized water
• water can be added into the resulting mixture at ⁇ 30° C. for hydrolysis. There are bubbles during hydrolysis process, and the hydrolysis process is not to be stopped until no bubbles come out.
• the resulting mixture is heated again to 20° C. to 40° C. and stirred for 5 h to 10 h. Subsequently, the resultant is separated and an organic phase therein is taken out.
• an organic solvent is preferably used for extraction of the inorganic phase in the resultant, and then the organic phase is combined with the organic phase obtained through separation, wherein useful organic solvents can be ethyl acetate, acetone, dichloromethane, or a mixture thereof, preferably dichloromethane.
• the solvent is removed from the organic phase or combined organic phase under reduced pressure prior to addition of nitrobenzene therein for reflux (for example at 210° C.) for 10 h to 48 h, preferably 15 h to 24 h. After that, the resultant is filtered, and the solvent is removed under reduced pressure.
• the molar ratio of 1,10-phenanthroline to nitrobenzene is in the range from 1:0.5 to 1:30, preferably from 1:15 to 1:20.
• Step b synthesis of 2-n-propyl-acyl-1,10-phenanthroline aminal ligand: the compound as shown in Formula (b′′) is reacted with the compound as shown in Formula (c) in the presence of p-toluenesulfonic acid as the catalyst to obtain the compound as shown in Formula (d′′).
• the product ligand as shown in Formula (d′′) is prepared by reacting 2-n-propyl-acyl-1,10-phenanthroline obtained in Step a with substituted anline as shown in Formula (c) in a container in the presence of an organic solvent containing no water or oxygen, wherein the molar ratio of 2-n-propyl-acyl-1,10-phenanthroline to substituted anline as shown in Formula (c) is in the range from 1:1 to 1:5.
• Said organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, mixtures thereof, etc., preferably toluene.
• the reaction is carried out under reflux in the presence of p-toluenesulfonic acid (p-TsOH) as the catalyst at, for example 110° C., wherein the mass ratio of p-TsOH to the total amount of the reactants (i.e., the compounds as shown in Formulae (b′′) and (c)) is in the range from 0.001:1 to 0.02:1; and the reaction time is in the range from 5 h to 10 h.
• the reaction is monitored by TLC.
• the solvent is removed under reduced pressure.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio therebetween in the range from 1:1 to 1:9, preferably 1:4 is used as an eluent to perform silica column chromatography to obtain the target product, i.e., the compound as shown in Formula (d′′).
• the target product is characterized by nuclear magnetism and mass spectrum.
• Step c synthesis of 2-n-propyl-acyl-1,10-phenanthroline aminal ferrous chloride complex: the compound as shown in Formula (d′′) is reacted with ferrous chloride to obtain the compound as shown in Formula (iii).
• ferrous chloride is dissolved into an organic solvent containing no water or oxygen, so as to form a solution with a concentration of 0.001 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• hydrated ferrous chloride FeCl 2 .4H 2 O
• ferrous chloride can also be used instead of ferrous chloride.
• 2-n-propyl-acyl-1,10-phenanthroline ligand (d′′) is separately dissolved into an organic solvent containing no water or oxygen to form a solution with a concentration of 0.01 g/ml to 0.1 g/ml, wherein the organic solvent can be selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane, and mixtures thereof, preferably tetrahydrofuran.
• the above two solutions are combined (for example at room temperature) under protection of an inner gas such as nitrogen, and the resulting mixture is stirred for some time under protection of an inert gas such as nitrogen, for example, being stirred overnight at room temperature.
• the reaction is monitored by TLC.
• conventional treatment methods of suction filtration, washing, drying, etc. are adopted to treat the reaction product to obtain the compound ligand as shown in Formula (iii). Said washing can be performed using an organic solvent such as anhydrous diethyl ether.
• the ligand is characterized by elemental analysis and infrared spectroscopy.
• the molar ratio of 2-n-propyl-acyl-1,10-phenanthroline ligand (d′′) to ferrous chloride is in the range from 1:1 to 1.2:1, preferably from 1.05:1 to 1.1:1.
• Ethylene is oligomerized in the presence of the above catalyst composition, which comprises imino ferrous complex shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• the above catalyst composition which comprises imino ferrous complex shown in Formula (I) as the main catalyst, an aluminum-containing cocatalyst, water, and an organic solvent.
• the catalyst composition has a content of water in the range from 5 to 450 ppm, preferably from 5 to 350 ppm, more preferably 20 to 260 ppm, and further preferably from 50 to 200 ppm.
• imino ferrous complex shown in Formula (I) as previously defined is adopted as the main catalyst.
• the mixing of the main catalyst and cocatalyst is performed in an atmosphere of ethylene (i.e., the main catalyst and cocatalyst are mixed in the presence of ethylene).
• the reaction temperature can be in the range from ⁇ 20° C. to 150° C., preferably from 0° C. to 80° C., and more preferably from 5° C. to 35° C.
• the reaction temperature can be in the range from ⁇ 20° C. to 150° C., preferably from 0° C. to 80° C., and more preferably from 5° C. to 50° C.
• the reaction pressure can be selected as 0.1 MPa to 30 MPa. Generally, the oligomerization activity improves as the pressure of ethylene increases.
• preferred ranges of varieties of organic solvents, varieties of cocatalysts, content of the main catalyst in view of the organic solvents, molar ratio of the cocatalysts to the main catalyst are correspondingly the same as those concerning the catalyst composition for ethylene oligomerization of the present disclosure.
• one specific embodiment of the process of ethylene oligomerization can comprise the following steps. (1) The reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system. (2) The reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere for the reaction system. (3) The catalyst composition including the main catalyst, the cocatalyst, water, and the organic solvent is added in the reaction system, followed by adequate stirring. (4) Ethylene is fed into the system to perform the oligomerization reaction, which is kept for 30 min to 100 min under 0.1 MPa to 30 MPa at ⁇ 20° C. to 150° C. (5) The reaction is stopped and the product is analyzed by gas chromatography (GC). In the present disclosure, in step (3), the main catalyst and cocatalyst can be added into the system after being dissolved into the organic solvent.
• GC gas chromatography
• products obtained therein include C 4 , C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 , etc., with selectivity of ⁇ -olefins thereof higher than 96%.
• the products are analyzed by GC. Results indicate that the oligomerization activity can be higher than 10 7 g ⁇ mol (Fe) ⁇ 1 .h ⁇ 1 .
• the remaining reaction mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid, no polymers can be obtained.
• the catalyst composition according to the present disclosure comprising imino ferrous complex shown in Formula (I) as the main catalyst, the aluminum-containing cocatalyst, water, and the organic solvent is used in ethylene oligomerization, a higher oligomerization activity can be acquired, with high selectivity of ⁇ -olefins, and rapid initiation, stable operation, and good repeatability of the reaction.
• a rather low ratio of Al/Fe or a low reaction temperature can still enable a high oligomerization activity.
• the present disclosure overcomes technical prejudices of persons skilled in the art and achieves unexpected technical effects.
• 2-formyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 is used as the main catalyst.
• reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system.
• the reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system.
• a reaction kettle is added with a certain amount of hydrous toluene, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of 2-formyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml.
• the content of water based on weight of the organic solvent is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• the activity of the catalyst for catalyzing the ethylene oligomerization is 0.51 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• the oligomers contain 22.3% of C 4 , 46.22% of C 6 to C 10 , 70.32% (wherein ⁇ -olefins account for 97.8%) of C 6 to C 18 , and 7.38% of C 20 to C 28 .
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• Table 1 The analysis results are shown in Table 1.
• Example 1 The steps in Example 1 are repeated only with different contents of water and reaction parameters. The data are shown in Table 1.
• Example 1 The steps of Example 1 are repeated only with 0 ppm of water. The data are shown in Table 1.
• the data in Table 1 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which contains water. More specifically, from comparisons between catalyst activity in Examples 1 to 7 to that in Comparative Example 1, it can be obvious seen that, under the same oligomerization conditions, the activity of the catalyst composition according to the present disclosure is 2.5 to 6 times of that of the catalyst used in Comparative Example 1. Furthermore, the examples according to the present disclosure obtain as high a selectivity of ⁇ -olefins as Comparative Example 1 does.
• the ethylene oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 . It is thus clear that the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• the oligomerization reaction according to the present disclosure is of rapid initiation, stable operation, and good repeatability.
• Table 1 shows that even when the ratio of Al to Fe is as low as 196, the catalyst of the present disclosure still has good activity for catalyzing the oligomerization reaction, thereby significantly reducing costs of ethylene oligomerization.
• the catalyst according to the present disclosure is of high practicability and has broad prospects for industrialization.
• Examples 5, 8, 9, and 10 prove that, according to the present disclosure, high oligomerization activity can still be obtained even at a low reaction temperature.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:2 is used as an eluent to perform silica column chromatography to the obtained black viscous liquid substance, so as to obtain a brown product, which weighs 1.9 g with a yield of 30%.
• the product, after nuclear magnetic resonance analysis and mass spectrometry, is determined as the compound as referred to under a), i.e., 2-acetyl-1,10-phenanthroline.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:4 is used as an eluent to perform silica column chromatography to obtain a bright yellow product, which weighs 0.61 g with a yield of 81%.
• the product, after nuclear magnetic resonance analysis, mass spectrometry, and elemental analysis, is determined as the compound as referred to under b), i.e., 2-acetyl-1,10-phenanthroline (2,6-diethylanil).
• the reaction is monitored by TLC until the 2-acetyl-1,10-phenanthroline (2,6-diethylanil) ligand substantially disappears.
• vacuum drying is performed to obtain a silver gray solid.
• the obtained solid is determined as the compound as referred to under c), i.e., 2-acetyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 , the elemental analysis of which is as follows.
• the ethylene oligomerization process comprises the following specific steps. (1) The reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system. (2) The reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system. (3) A reaction kettle is added with of water and toluene as solvents, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of 2-acetyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml, wherein based on weight of the organic solvent (i.e., toluene), the content of water is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• the oligomers contain 28.21% of C 4 , 56.41% of C 6 to C 10 , 69.77% (wherein ⁇ -olefins account for 98.1%) of C 6 to C 18 , and 2.01% of C 20 to C 28 .
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• the analysis results are shown in Table 2.
• Example 13 The steps in Example 13 are repeated only with different contents of water and reaction parameters. The data are shown in Table 2.
• Example 13 The steps of Example 13 are repeated only with 0 ppm of water. The data are shown in Table 2.
• the data in Table 2 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which comprises the main catalyst, i.e., the 2-acetyl-1,10-phenanthroline (anil) FeCl 2 complex, the aluminum-containing cocatalyst, water, and the organic solvent. Moreover, high selectivity of ⁇ -olefins, and rapid initiation, stable operation, and good repeatability of the oligomerization reaction can be obtained. Particularly, When the content of water ranges from 50 ppm to 200 ppm, the ethylene to oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production. Moreover, even when the ratio of Al to Fe is rather low, a good oligomerization activity can still be obtained. In addition, according to the present disclosure, high oligomerization activity can still be obtained at a low reaction temperature.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:2 is used as an eluent to perform silica column chromatography to the obtained black viscous liquid substance, so as to obtain a brown product, which weighs 2.0 g with a yield of 30%.
• the product, after nuclear magnetic resonance analysis and mass spectrometry, is determined as the compound as referred to under a), i.e., 2-n-propyl-acyl-1,10-phenanthroline.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:4 is used as an eluent to perform silica column chromatography to obtain a bright yellow product, which weighs 0.63 g with a yield of 81%.
• the product, after nuclear magnetic resonance analysis, mass spectrometry, and elemental analysis, is determined as the compound as referred to under b)), i.e., 2-n-propyl-acyl-1,10-phenanthroline (2,6-diethylanil).
• Elemental analysis C 25 H 25 N 3 (367.49). Theoretical value: C, 81.71; H, 6.86; N, 11.43. Measured value: C, 81.66; H, 6.87; N, 11.47.
• the reaction is monitored by TLC until the 2-n-propyl-acyl-1,10-phenanthroline (2,6-diethylanil) ligand substantially disappears.
• vacuum drying is performed to obtain a silver gray solid.
• the obtained solid is determined as the compound as referred to under c), i.e., 2-n-propyl-acyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 , the elemental analysis of which is as follows.
• a stainless steel autoclave is added with toluene, water, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml) as the cocatalyst, and 2 ml of a toluene solution of 2-n-propyl-acyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 (with a concentration of 2.5 ⁇ mol/ml) as the main catalyst.
• the total amount of the composition is 100 ml, wherein the ratio of Al/Fe is 196, and based on weight of toluene, the content of water is 5 ppm.
• the oligomerization activity is 0.57 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• the oligomers contain 12.92% of C 4 , 42.13% of C 6 to C 10 , 73.32% (wherein ⁇ -olefins account for 97.6%) of C 6 to C 18 , and 13.76% of C 20 to C 28 .
• the value of K is 0.63.
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• Table 3 The analysis results are shown in Table 3.
• Example 25 The steps in Example 25 are repeated only with different contents of water and reaction parameters. The data are shown in Table 3.
• Example 25 The steps of Example 25 are repeated only with 0 ppm of water. The data are shown in Table 3.
• the data in Table 3 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which comprises the main catalyst, i.e., the complex of 2-n-propyl-acyl-1,10-phenanthroline (anil) FeCl 2 , the aluminum-containing cocatalyst (such as Et 3 Al), water, and the organic solvent. Moreover, high selectivity of ⁇ -olefins can be obtained. Besides, even when the ratio of Al to Fe is rather low, the catalyst of the present disclosure still possesses good oligomerization activity, and high oligomerization activity can still be obtained at a low reaction temperature.
• the main catalyst i.e., the complex of 2-n-propyl-acyl-1,10-phenanthroline (anil) FeCl 2 , the aluminum-containing cocatalyst (such as Et 3 Al), water, and the organic solvent.
• the ethylene oligomerization activity approaches or exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 . It is thus clear that the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• 2-butyryl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 is used as the main catalyst.
• reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system.
• the reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system.
• a reaction kettle is added with a certain amount of hydrous toluene, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of 2-butyryl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml.
• the content of water based on weight of the organic solvent is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• the activity of the catalyst for catalyzing the ethylene oligomerization is 0.57 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 ⁇ h ⁇ 1 .
• the oligomers contain 40.66% of C 4 , 47.77% of C 6 to C 10 , 58.25% (wherein ⁇ -olefins account for 97.2%) of C 6 to C 18 , and 1.09% of C 20 to C 28 .
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• Table 4 The analysis results are shown in Table 4.
• Example 37 The steps in Example 37 are repeated only with different contents of water and reaction parameters. The data are shown in Table 4.
• Example 37 The steps of Example 37 are repeated only with 0 ppm of water. The data are shown in Table 4.
• the data in Table 4 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which contains water. More specifically, from comparisons between the catalyst activity in Examples 37 to 43 to that in Comparative Example 4, it is obvious that, under the same oligomerization conditions, the activity of the catalyst composition according to the present disclosure is 1.8 to 4 times of that of the catalyst used in Comparative Example 4. Furthermore, the examples according to the present disclosure obtain as high a selectivity of ⁇ -olefins as Comparative Example 4 does. Particularly, when the content of water ranges from 50 ppm to 200 ppm, the ethylene oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 ⁇ h ⁇ 1 .
• the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• the oligomerization reaction according to the present disclosure is of rapid initiation, stable operation, and good repeatability.
• Table 4 shows that even when the ratio of Al to Fe is as low as 196, the catalyst of the present disclosure still has good activity for catalyzing the oligomerization reaction, thereby significantly reducing costs of ethylene oligomerization.
• the catalyst according to the present disclosure is of high practicability and has broad prospects for industrialization.
• the examples prove that according to the present disclosure, high oligomerization activity can still be obtained even at a low reaction temperature.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:2 is used as an eluent to perform silica column chromatography to the obtained black viscous liquid substance, so as to obtain a brown product, which weighs 2.1 g with a yield of 30%.
• the product, after nuclear magnetic resonance analysis and mass spectrometry, is determined as the compound as referred to under a), i.e., 2-isobutyryl-1,10-phenanthroline.
• a mixture solution of ethyl acetate and petroleum ether with a volume ratio of 1:4 is used as an eluent to perform silica column chromatography to obtain a bright yellow product, which weighs 0.65 g with a yield of 81%.
• the product, after nuclear magnetic resonance analysis, mass spectrometry, and elemental analysis, is determined as the compound as referred to under h), i.e., 2-isobutyryl-1,10-phenanthroline (2,6-diethylanil).
• the reaction is monitored by TLC until the 2-isobutyryl-1,10-phenanthroline (2,6-diethylanil) ligand substantially disappears.
• vacuum drying is performed to obtain a silver gray solid.
• the obtained solid is determined as the compound as referred to under c), i.e., 2-isobutyryl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 , the elemental analysis of which is as follows.
• the ethylene oligomerization reaction specifically comprises the following steps. (1) A stainless steel reaction kettle is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system. (2) The reaction kettle is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system. (3) The reaction kettle is added with water and toluene under adequate stirring. (4) 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 mol/ml) is added into the reaction kettle.
• the oligomerization activity is 0.52 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• the oligomers contain 20.6% of C 4 , 48.49% of C 6 to C 10 , 72.24% (wherein ⁇ -olefins account for 98.2%) of C 6 to C 18 , and 7.15% of C 20 to C 28 .
• the value of K is 0.63.
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• Table 5 The analysis results are shown in Table 5.
• Example 49 The steps in Example 49 are repeated only with different contents of water and reaction parameters. The data are shown in Table 5.
• Example 49 The steps of Example 49 are repeated only with 0 ppm of water. The data are shown in Table 5.
• the data in Table 5 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which comprises the main catalyst, i.e., the 2-isobutyryl-acyl-1,10-phenanthroline (anil) FeCl 2 complex, the aluminum-containing cocatalyst (such as Et 3 Al), water, and the organic solvent. Moreover, high selectivity of ⁇ -olefins can be obtained. Besides, even when the ratio of Al to Fe is rather low or when the reaction temperature is low, the oligomerization activity is still high.
• the main catalyst i.e., the 2-isobutyryl-acyl-1,10-phenanthroline (anil) FeCl 2 complex
• the aluminum-containing cocatalyst such as Et 3 Al
• the ethylene oligomerization activity approaches 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 . It is thus clear that the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• 2-benzoyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 is used as the main catalyst.
• reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system.
• the reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system.
• a reaction kettle is added with a certain amount of hydrous toluene, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of 2-benzoyl-1,10-phenanthroline (2,6-diethylanil) FeCl 2 (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml.
• the content of water based on weight of the organic solvent is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• the activity of the catalyst for catalyzing the ethylene oligomerization is 0.52 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• the oligomers contain 21.44% of C 4 , 52.41% of C 6 to C 10 , 74.05% (wherein ⁇ -olefins account for 98%) of C 6 to C 18 , and 4.51% of C 20 to C 28 .
• the remaining mixture is neutralized by an ethanol solution acidified with dilute hydrochloric acid of 5%, and no polymers are obtained.
• Table 6 The analysis results are shown in Table 6.
• Example 61 The steps in Example 61 are repeated only with different contents of water and reaction parameters. The data are shown in Table 6.
• Example 61 The steps of Example 61 are repeated only with 0 ppm of water. The data are shown in Table 6.
• the data in Table 6 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which contains water. More specifically, from comparisons between catalyst activity in Examples 61 to 67 to that in Comparative Example 6, it is obvious that, under the same oligomerization conditions, the activity of the catalyst composition according to the present disclosure is 2 to 4.5 times of that of the catalyst used in Comparative Example 6. Furthermore, the examples according to the present disclosure obtain as high a selectivity of ⁇ -olefins as Comparative Example 6 does, Particularly, when the content of water ranges from 50 ppm to 200 ppm, the ethylene oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 .
• a catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• the oligomerization reaction according to the present disclosure is of rapid initiation, stable operation, and good repeatability.
• Table 6 shows that even when the ratio of Al to Fe is as low as 196, the catalyst of the present disclosure still has good activity for catalyzing the oligomerization reaction, thereby significantly reducing costs of ethylene oligomerization.
• the catalyst according to the present disclosure is of high practicability and has broad prospects for industrialization.
• the examples prove that, according to the present disclosure, high oligomerization activity can still be obtained even at a low reaction temperature.
• a 2,6-diacetyl pyridine (o-toluid) FeCl 2 complex is used as the main catalyst.
• reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system.
• the reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system.
• a reaction kettle is added with a certain amount of hydrous toluene, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of the 2,6-diacetyl pyridine (o-toluid) FeCl 2 complex (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml.
• the content of water based on weight of the organic solvent is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• Example 73 The steps in Example 73 are repeated only with different contents of water and reaction parameters. The data are shown in Table 7.
• Example 73 The steps of Example 73 are repeated only with 0 ppm of water. The data are shown in Table 7.
• the data in Table 7 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which comprises the main catalyst, i.e., the 2,6-diacetyl pyridine (o-toluid) FeCl 2 complex, the aluminum-containing cocatalyst (such as Et 3 Al), water, and the organic solvent. Moreover, high selectivity of ⁇ -olefins can be obtained.
• the catalytic activity of the oligomerization reaction system reaches as high as 1.56 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 , which is 10 times higher than the catalytic activity under the same conditions only with the catalyst containing no water.
• the oligomerization activity is still high.
• the content of water ranges from 50 ppm to 200 ppm
• the ethylene oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 . It is thus clear that the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• a 2-benzoxazolyl-6-acetyl (2,6-diethylanil) FeCl 2 complex is used as the main catalyst.
• reaction system is replaced through operations such as high temperature drying, vacuum replacement, etc., so as to ensure an anhydrous and oxygen-free reaction system.
• the reaction system is replaced with ethylene, so as to ensure an ethylene atmosphere in the reaction system.
• a reaction kettle is added with a certain amount of hydrous toluene, 1.37 ml of a toluene solution of Et 3 Al (with a concentration of 715 ⁇ mol/ml), and 2 ml of a toluene solution of the 2-benzoxazolyl-6-acetyl (2,6-diethylanil) FeCl 2 complex (with a concentration of 2.5 ⁇ mol/ml).
• the total amount of the composition is 100 ml.
• the content of water based on weight of the organic solvent is 5 ppm, and the ratio of Al/Fe is 196.
• ethylene is fed into the kettle to perform the oligomerization reaction.
• the oligomerization reaction is kept for 30 min under an ethylene pressure of 1 MPa at 30° C.
• the reaction is stopped, and a small amount of reaction product is taken out for gas chromatography (GC) analysis.
• GC gas chromatography
• Example 85 The steps in Example 85 are repeated only with different contents of water and reaction parameters. The data are shown in Table 8.
• Example 85 The steps of Example 85 are repeated only with 0 ppm of water. The data are shown in Table 8.
• the data in Table 8 indicate that a high ethylene oligomerization activity is obtained in the presence of the catalyst composition according to the present disclosure which comprises the main catalyst, i.e., the 2-benzoxazolyl-6-acetyl (2,6-diethylanil) FeCl 2 complex, the aluminum-containing cocatalyst (such as Et 3 Al), water, and the organic solvent. Moreover, high selectivity of ⁇ -olefins can be obtained.
• the catalytic activity of the oligomerization reaction system reaches as high as 1.08 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 , which is 10 times higher than the catalytic activity under the same conditions only with the catalyst containing no water.
• the oligomerization activity is still high.
• the content of water ranges from 50 ppm to 200 ppm
• the ethylene oligomerization activity exceeds 1 ⁇ 10 7 g ⁇ mol(Fe) ⁇ 1 .h ⁇ 1 . It is thus clear that the catalyst having a content of water within the above range is especially suitable for catalyzing ethylene oligomerization in industrial production.
• the catalyst composition according to the present disclosure can promote a high oligomerization activity, with high selectivity of ⁇ -olefins. Even the oligomerization is carried out with rather a low ratio of Al/Fe or at a low reaction temperature, high oligomerization activity can still be obtained.

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